Antistatic softening composition containing a quaternary ammonium salt and a ethenoxy quaternary ammonium salt

ABSTRACT

An antistatic softening composition, comprising 4-10 percent by weight of a quaternary ammonium salt of general formula (I):   wherein R1 and R2 each represent an alkyl group of C14-C22, R3 and R4 each represent an alkyl group of C1-C3, benzyl group or (C2H4O)nH (n 1 - 3) and X represents Cl, Br or C2H5SO4, 0.1-5 percent by weight of an ethenoxy quaternary ammonium salt of general formula (II):   wherein R5 represents an alkyl group of C10-C22, R6 represents an alkyl group of C1-C3 or benzyl group, X represents Cl, Br or C2H5SO4 and m and n each represent an integer of more than 1 inclusive, with the proviso that m +. n is 20-100, and 0.5-15 percent by weight of one or more additives selected from the group consisting of alcohols of lower than C3 inclusive, glycols, glycerol, sorbitol and urea.

United States Patent [191 Katsumi et al.

[ Nov. 26, 1974 1 ANTISTATIC SOFTENING. COMPOSITION CONTAINING A QUATERNARY AMMONIUM SALT AND A ETHENOXY QUATERNARY AMMONIUM SALT [75] Inventors: Mamoru Katsumi; Toshio Sato, both of Wakayama, Japan [73] Assignee: Kao Soap Co. Ltd., Chuo-ku,

Tokyo, Japan [22] Filed: Sept. 19, 1972 [21] Appl. No.: 290,345

[30] Foreign Application Priority Data Primary Examiner-Stephen .1. Lechert, Jr. Attorney, Agent, or Firm-Woodhams, Blanchard and Flynn [57] ABSTRACT An antistatic softening composition, comprising 4-10 percent by weight of a quaternary ammonium salt of general formula (1):

R; R, [y Rt Rt (I) wherein R and R each represent an alkyl group of C,,C R and R each represent an alkyl group of C, -C benzyl group or (C H,O),,H (n 1 3) and X represents Cl, Br or C H SO),, 0.1-5 percent by weight of an ethenoxy quaternary ammonium salt of general formula (11):

(CHzCHzO) H (II) wherein R represents an alkyl group of C, ,-C R, represents an alkyl group of C -C or benzyl group, X represents Cl, Br or C H SO, and m and n each represent an integer of more than 1 inclusive, with the proviso that m n is 20-100, and 05-15 percent by weight of one or more additives selected from the group consisting of alcohols of lower than C inclusive, glycols, glycerol, sorbitol and urea.

7 Claims, No Drawings ANTISTATIC SOFTENING COMPOSITION CONTAINING A QUATERNARY AMMONIUM SALT AND A ETI-IENOXY QUATERNARY AMMONIUM SALT BACKGROUND OF THE INVENTION 1. FIELD OF THE INVENTION The present invention relates to a softening composition which is stable even at a high concentration and which imparts an excellent antistatic property to the treated textile products.

2. DESCRIPTION OF THE PRIOR ART Softening agents have been used frequently as finishing agents for textile products. They are used mainly for finishing of washed underwear and diapers to impart a soft feeling to the textile products. Important properties required of softening agents are as follows:

a. to impart a soft feeling to the treated textile products,

b. to impart antistatic property to the treated textile products,

c. not to reduce hygroscopicity of the treated textile products, and.

d. to maintain stability and low viscosity even at a high concentration of the softening agent solution against possible environmental changes.

Among the above four properties, (a) is indispensable of course and most important, while properties (b) through (d) are also significant in practice.

Various compositions of softening agents have. been known, but most of them contain quaternary ammonium salts having two long chain alkyl groups as their main ingredients.

Further, some of the known compositions contain, in addition to said main ingredient, a nonionic surfactant such as an alkylphenol ethylene oxide adduct and a solvent such as an alcohol or glycol to improve the stability of the solution. Although satisfactory softening effects can be obtained by using such known compositions, the properties and (d), particularly the antistatic property and stability of them are still insufficient.

Recently, the use of fabrics for clothing made of synthetic fibers has been increasing more and more. However, as compared with fabrics of natural fibers, they have serious shortcomings in that they are apt to have a static electric charge, which results in dusty clothing, clinging of the clothing to the body and sparking at the time of putting on or pulling off of the clothing. These serious shortcomings of synthetic fiber clothing fabrics are well known.

Further, during the storage of softening agent solutions under various climate and temperature conditions, an increase in the viscosity of the solution or a,

phase separation is undesirable. In addition, it is desired that the softening agents do not freeze at a low temperature around the freezing point, or even if they are frozen, their viscosities are recovered when the temperature is elevated again to room temperature.

It is expedient to incorporate an antistatic agent for obtaining a composition having an antistatic property. However, if a conventionally known antistatic agent such as stearyl trimethylammonium chloride is incorporated in a softening agent composition containing a quaternary ammonium salt having two long chain alkyl SUMMARY OF THE INVENTION The present invention relates to a softening composi tion having an excellent softening effect, particularly a sufficientstability even at a high concentration, and an excellent antistatic effect upon treated textile products.

The present invention-relates to an antistatic softeningcomposition characterized by containing 4-10 percent by weight of a quaternary ammonium salt represented by the following general formula (1):

wherein R and R each represent an alkyl group of C -C R and R each represent an alkyl group of C -C benzyl group or (C H O),,H (n 1 3) and X represents Cl, Br or C I-I SO. 0.1-5 percent by weight of ethenoxy quaternary ammonium salt represented'by the following general formula (II):

wherein R represents an alkyl group of C -C R represents an alkyl group of C,-C or benzyl group, X represents Cl, Br or C I-I SO and m and n each represent an integer of more than 1 inclusive, with the priviso than "1+" is 20-100 and 0.5-15 percent by weight of one or more additives selected from the group consisting of alcohols of lower than C inclusive, glycols, glycerol, sorbitol and urea.

Now a description will be made of particularly preferred compositions. Preferred R and R are C -C alkyl groups and preferred R and R are C -C alkyl groups and benzyl group. Preferred R are those of C -C and the sum of m and n is preferably 30-70. Preferred additives and propylene glycol, ethylene glcol and glycerol. The preferred amount of the ethenoxy quaternary ammonium salt of the above general formula (II) is 1.0-5.0 percent by weight and the preferredamount of the additives is 3-8 percent by weight; vThe most preferred quaternary ammonium salts of the above general formula (I) are distearyl dimethylammonium chloride and dihydrogenated tallowalkyl dimethylammonium chloride. Though the object of the invention can be attained sufficiently with preferably incorporated therein for ensuring the stability of the composition for a long period.

The present invention will be illustrated more concretely by way of examples.

EXAMPLE 1 (This example is to demonstate the effects based on the constituents of the compositions.)

Among the compositions shown in Table 1 given below, the compositions A through G are those of the present invention and the compositions H through K are comparative ones. Percentages in the table are shown in weight and the remainder is the amount of water.

Viscosity, antistatic property and softening property shown in Table l are measured according to the methods which will be described below. The results of the measurements are shown by four grades of G, O, A and X,@ being the most excellent (the lowest in viscosity). Quaternary ammonium salts in the table are compounds of the general formula (I) and the ethenoxy quaternary salts are ethenoxy quaternary ammonium salts of the general formula (ll). The symbol E indicates ethylene oxide.

METHODS OF MEASUREMENT l. Viscosity:

The composition directly after blending was allowed to stand at room temperature for 6 months and then at 50 C for 3 months, frozen at 30 C, thawed at room temperature and then frozen again. This procedure was repeated 5 times. Four samples of each composition were measured at 30 C with Brookfield type viscometer. The unit of numerals in the table is centi-poises.

2. Antistatic property:

Every swatch made from polyester fiber or acrylic fiber was immersed in 0.1 percent or 0.3 percent solution of each softening composition (weight ratio of the composition to the treating solution 1:20) and it was stirred and treated for 5 minutes. The solutions were squeezed out at 100 percent squeeze ratio. The swatches were dried and then allowed to stand at 25 C under percent humidity for 2 days to obtain the samples. The results of frictional static voltage mea sured with a rotatory static tester (the model by the Chemical Laboratory for Kyoto University) are shown in Table 2. Generally, at a frictional static voltage of less than 300 V, a drawback due to the static electricity is negligible. In this connection, frictional static voltages of untreated swatches of polyester and acrylic fibers were 2,200 V and 1,900 V, respectively.

3. Softening property:

Pieces of cotton towel, cotton plain fabric for diaper and blanket made from polyacrylonitrile fiber were washed in a usual manner, treated with 0.1 percent and 0.3 percent solutions of each softening composition and finally dried. The samples were tested by 5 men and 5 women according to handling (tactile impression) and their feelings were evaluated by the points compared with the standard criteria. The numerals in Table 2 are the sums of the points. The larger the nu meral, th softer the textile.

Table l Ethenoxy quaternary Com- Quaternary ammonium salt or another Additive Vis- Antistatic Softposition salt quaternary salt cosity property ness A Distearyldimethyl Stearylmethyl Pro- Q Q Q ammonium chloride dipolyoxyethylene pylene ammonium chloride glycol containing 7.0 moles of B0 2.2 6.0 B Distearyldimcthyl Stearylmethyl Pro- Q Q Q ammonium chloride dipoloxyethylene pylene NaCl ammonium chloride containing 50 7.0 moles of EO 2.2 6.0 0.02 c Distearyldimethyl Behenylbenzyldi- O O Q ammonium chloride polyoxyethylene Ethylene ammonium chloride glycol NaBr containing 40 6.0 moles of B0 2.0 7.0 0.03 D Dibchcnyldimcthyl Stearylmethyl Q Q 0 ammonium bromide dipolyoxyethylcne Glycerol NaCl ammonium bromide containing 30 5.0 moles of EO L5 3.0 0.05 E Distearyldihydroxy- Laurylpropyldi- Ethanol NaBr O O 0 ethylammonium polyoxycthylcnc ethosulfatc ammonium chloride containing 7.0 moles of B0 2.5 7.0 0.03 F Dihydrogenated Stearylcthyldi- Sorbitol NaCl Q Q Q tallowalkyl dipolyoxyethylenc methyl ammonium ammonium ethochloride sulfate containing 50 6.0 moles of E0 L0 4.0 0.02 G Dipalmitylbenzyl Stearylmethyldi- Urea Q Q Q methyl ammonium polyoxyethylene 3.0

chloride ammonium chloride Na SO,

containing [00 Pro- 8.0 moles of B0 3.0 pylenc glycol 3.0 0.03 H Dihydrogcnated Stearylmethyldi- Protallowalkyl di polyoxyethylcnc pylcne NaCl methyl ammonium ammonium chloride glycol A Q A chloride containing 8 7.0 moles of E0 [.5 5.0 0.03 l Dihydrogenated Stearyltrimcthyl Protallowalkyl diammonium chloride pylene NaCl methyl ammonium glycol X 0 O chloride Table 1 Continued Ethenoxy quaternary 1 Com- Quaternary ammonium salt or another Additive Vis- Antistatic Softpos1t1on salt quaternary salt cosity property ness .l Dihydrogenated Distearylmethyl Protallowalkyl dipolyoxycthylene pylenc NaCl methyl ammonium ammonium chloride glycol A A O chloride containing 40 7.0 moles of E 2.0 5.0 0.03 K Dihydrogenated Nonylphenolpoly- Protallowalkyl dioxyethylene ether pylcne NaCl methyl ammonium containing 50 glycol O X A chloride 7.0 moles of E0 L0 5.0 0.03

Table 2 Viscosity (centi-poises) Antistatic property Softness (volts) Comimmediately Room temp. 50C 30C Polyester Acrylic position after 6 months 3 months freeze blending 5 times 0.1% 0.3% 0.1% 0.3% 0.l% 0.3%

A 50 170 58 H0 110 75 185 70 100 98 B 50 52 48 40 l 80 I90 66 98 98 C 46 44 46 51 74 62 130 60 97 99 D 64 62 58 58 88 66 100 78 98 97 E 120 145 111 X90 78 66 110 83 l00 97 F 150 145 150 170 85 61 142 70 97 97 G 118 l 145 146 73 S7 96 60 98 98 H 104 270 243 756 130 100 I70 110 90 90 l 350 710 2400 4600 500 370 370 290 79 69 .l 610 590 410 2200 1550 890 900 610 78 81 K H8 135 145 1200 1000 8 I0 830 530 69 72 EXAMPLE 2 and measured at 30 C w1th a Brookfield type v1scome- (This example is to demonstrate the effects based on the proportions of constituents of the compositions.)

Effects of changes in the ethylene oxide units 'of ethenoxy quaternary salts and effects of additives (such as propylene glycol) were examined to obtain the results as shown in Table 3.

METHODS OF MEASUREMENT:

1. Viscosity The composition immediately after the blending was allowed to stand at room temperature for one month ter. The unit of numerals in the table is centi-poises.

2. Recovery after freeze The samples were frozen by allowing them to stand .at C for one day, and thawed by elevating the temperature to a room temperature. This procedure was repeated five times and the state of the samples was examined.

3. Dispersion stability The samples were allowed to stand in a constant temperature bath at 50 C for one month and the phase separation was examined.

The results of evaluation of the above items (2) and (3) were shown by four grades (in the same manner as in Example 1).

The same tendency as in Table 3 was observed also with other ethenoxy quaternary salts, i.e., behenylethyldipolyoxethylene ammonium ethosulfate and laurylbenzyldipolyoxyethylene ammonium chloride. In Table 3, the numerals in the column 1 indicate the numbers of the ethylene oxide unit in 1 mole of the molecule and those in the line 2 indicate wt. percent of PG added.

Table 3 G Viscosity at room temperature Recovery after freeze Dispersion stability P E0 0 3 5 10 15 20 0 5 10 15 20 0 3 5 10 15 20 2 3600 1120 750 460 860 980 A A A A A A A A A A A A 8 125 90 104 180 420 1390 A 6 O 6 A A 6 A A A A 20 114 72 80 75 240 1350 A 8 A A O A 84 102 80 80 140 1440 A O O A A O A 70 110 105 1750 A O 0 1 8 A O I O A 50 H8 52 48 98 2250 A O O y A O 1 o 8 A 60 240 190 51 53 110 2500 A O 0 O A o 0' A 976 540 5:18 230 240 2410 A A O O A A O O O A 780 558 414 390 410 2400 A A O O A A A O O O O A 710 690 390 440 610 2250 A A O O A A A O O O A A 1200 1100 980 780 830 2150 A A A A A A A A A A A A none 12000 9800 3700 1200 1100 980 x x x A A A x A O Q A A The embodiments of the invention in which the exclusive property or privelege is claimed are defined as follows:

1. An antistatic softening composition, consisting essentially of 4-10 percent by weight of a quaternary ammonium salt of the formula (1):

weight of an ethenoxy quaternary ammonium salt of the formula (II):

wherein R represents an alkyl group of C -C R represents an alkyl group of C -C or benzyl group, X represents Cl, Br or C H SO and m and n each represent an integer of more than 1 inclusive, with the privisio that m n is 20-100, 0.5 percent by weight of one or more additives selected from the group consist ing of alcohols of lower than C inclusive, glycols, glycerol, sorbitol and urea, the balance of said composition being water.

2. An antistatic softening composition according to claim 1, in which R and R each represents an alkyl group of C -C R and R each represents an alkyl group of C -C or benzyl group, R represents an alkyl group of C -C and the sum of m and n is 30-70.

3. An antistatic softening composition according to claim 1, in which the additive is selected from propylene glycol, ethylene glycol and glycerol.

4. An antistatic softening composition according to claim 1, in which the amount of said ethenoxy quaternary ammonium salt of the formula (II) is 1.0 to 5.0 percent by weight.

5. An antistatic softening composition according to claim 1, in which the amount of the additive is 3 to 8 percent by weight.

6. An antistatic softening composition according to claim 3, in which the amount of the additive is 3 to 8 percent by weight.

7. An antistatic softening composition according to claim 1, in which said quaternary ammonium salt of the formula (I) is selected from distearyldimethylammonium chloride and dihydrogenated tallowalkyl dimethylammonium chloride. 

1. AN ANTISTATIC SOFTENING COMPOSITION, CONSISTING ESSENTIALLY OF 4-10 PERCENT BY WEIGHT OF A QUATERNARY AMMONIUM SALT OF THE FORMULA (I):
 2. An antistatic softening composition according to claim 1, in which R1 and R2 each represents an alkyl group of C16-C18, R3 and R4 each represents an alkyl group of C1-C3 or benzyl group, R5 represents an alkyl group of C12-C18 and the sum of m and n is 30-70.
 3. An antistatic softening composition according to claiM 1, in which the additive is selected from propylene glycol, ethylene glycol and glycerol.
 4. An antistatic softening composition according to claim 1, in which the amount of said ethenoxy quaternary ammonium salt of the formula (II) is 1.0 to 5.0 percent by weight.
 5. An antistatic softening composition according to claim 1, in which the amount of the additive is 3 to 8 percent by weight.
 6. An antistatic softening composition according to claim 3, in which the amount of the additive is 3 to 8 percent by weight.
 7. An antistatic softening composition according to claim 1, in which said quaternary ammonium salt of the formula (I) is selected from distearyldimethylammonium chloride and dihydrogenated tallowalkyl dimethylammonium chloride. 